JPH09132443A - Cement admixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high fluidity by incorporating a glycidyl ether adduct of polyoxyalkylene diamine, a compd. capable of formaldehyde cocondensation with the adduct, the compd. capable of forming sulfonic acid, and formaldehyde. SOLUTION: At least one kind of monomers capable of formaldehyde cocondensation and expressed by formula I, II and III (X1 , X3 , X5 and X6 are each H, CH2 SO3 Y, etc.; Y is alkali metal, ammonium, etc.; R3 is H or 1-6C alkyl; X4 is sulfon, amine salt, etc.) in an amount of 1mol, 1-6mol formaldehyde and water are allowed to react at about 60-90 deg.C. Then, 0.005-0.5mol glycidyl ether adduct of polyoxyalkylene diamine expressed by formula IV (R1 is 1-5C alkyl, R2 is H, 1-10C alkyl, etc.; A0 and B0 are each 2-5C oxyalkylene; (m) and (n) are each 0-100, 100>=(m+n)>=4) and about 0.3-4mol compd. such as Na2 SO3 capable of forming the sulfonic group are added and allowed to react under weakly acidic condition and kept in a prescribed viscosity to obtain a cement admixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an admixture for a cement or a cement composition, and more particularly, to the addition of a hydraulic cement composition such as a cement paste, mortar, concrete or the like when kneading to improve the workability. The present invention relates to a cement admixture to be improved.

[0002]

2. Description of the Related Art Conventionally, various kinds of organic compounds, especially cement water reducing agents, added to cement are known. As typical ones, salts of β-naphthalene sulfonic acid formaldehyde high condensation product, melamine sulfonic acid formaldehyde condensation product, lignin sulfonate, oxycarboxylic acid, amino sulfonate condensate, etc. are known. . When these compounds are added to a kneaded product composed of cement, water and aggregate, sufficient workability can be obtained even if the amount of water during kneading is reduced. Therefore, there is an advantage that workability is improved, and since the water-cement ratio can be reduced, it is useful for enhancing the strength of a hydraulic cement composition such as cement paste, mortar, and concrete.

[0003] However, in general, cement paste,
Mortar, hydraulic cement composition such as concrete,
With the passage of time after kneading, the fluidity is lost. This phenomenon occurs when the organic compound added as the cement water reducing agent is used, and particularly, β-
This is remarkable when a salt of a highly condensed naphthalenesulfonic acid formaldehyde or the like is used, and depending on the composition of the concrete, a phenomenon in which the slump is reduced to half or less within 30 minutes after kneading is observed. Due to the phenomenon that the slump loss is large, the following problems occur. In other words, the concrete composition may be pumped by pumping concrete, but if the pumping is temporarily interrupted due to a break time or various troubles at that time, the pumping pressure may suddenly increase when resuming, And piping may be blocked. Also, due to reduced fluidity, the compact may not be sufficiently compacted in the mold and a defective portion may be generated.

In order to suppress slump loss, various water reducing agents have been developed in the past. For example, a substance in which the functional group is dissociated by an alkali in concrete, a so-called sustained-release high-performance water reducing agent (Japanese Patent Publication No. 63-5346) is known. Further, a water-soluble vinyl copolymer (Japanese Patent Publication No. 6-60042) is known, in which a new functional group appears by being hydrolyzed in an alkali and suppresses slump loss. Further, for the purpose of maintaining a slump due to steric hindrance of a molecular chain, a polyalkylene glycol monoester monomer having an unsaturated bond and a (meth) acrylic acid monomer and / or an unsaturated dicarboxylic acid monomer (JP-B-59-18338, JP-B-2)
JP-B-7897, JP-B-2-7898, JP-B-2-7901, JP-B-2-8983, JP-B2-111542, JP-B5-111057, and JP-B6-88817. And water-soluble vinyl copolymers (these are generically referred to as polycarboxylic acid type). Further, a condensate in which a polyalkylene glycol chain is introduced into an aromatic compound (Japanese Patent Laid-Open No. 6-3 / 1994)
No. 40459) has also been recently developed.

[0005]

However, while these compounds show an excellent flow effect, they have various problems. First, in the case of sustained-release type high-performance water reducing agents that act with alkali in concrete and water-soluble vinyl copolymers that are newly hydrolyzed to replenish functional groups and suppress slump loss, the carboxyl groups will change over time. Will appear. This carboxyl group has a strong binding force with calcium ions. Therefore, these compounds have a problem in that they capture calcium ions in the cement and increase the setting delay.

Furthermore, a polycarboxylic acid having an oxyalkylene chain in the molecule has high air entrainment, and it is difficult to control the amount of air in concrete. In reality, the amount of air is controlled using an antifoaming agent, but the amount of air fluctuates greatly depending on the kneading conditions in the concrete mixer, the agitator conditions of the mixer truck, and the transport time,
There is a problem that it is difficult to use. Furthermore, (meta)
Since copolymerization is carried out using acrylic acid-based monomers and / or unsaturated dicarboxylic acid-based monomers, these compounds have a carboxyl group in the molecule. However, there is a problem that is increased. That is, the initial strength of the cement mortar or concrete decreases. In addition, when a large slump is used, that is, when soft mortar or concrete is used, material separation may occur, which is a problem.

Further, a condensate in which a polyalkylene glycol chain is introduced into an aromatic compound has a problem that a flow effect similar to that of a polycarboxylic acid having an oxyalkylene chain in a molecule cannot be recognized.

[0008]

The inventors of the present invention have conducted extensive studies in order to solve these problems, and as a result, have found that a cocondensate having a certain specific molecular structure does not cause a significant delay in curing and exhibits excellent dispersion. The present invention has been completed by showing the effect and the slump holding effect and further having the remarkable material separation resistance.

That is, the present invention provides a glycidyl ether adduct (A) to a polyoxyalkylene diamine, a glycidyl ether adduct (A) to a polyoxyalkylene diamine, and a monomer (B) capable of co-condensing formaldehyde.
And a cement admixture comprising a co-condensate containing a compound (C) that forms a sulfonic group and formaldehyde.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. General formula (l) Here, R ₁ : an alkyl group having 1 to 5 carbon atoms R ₂ : H, an alkyl group having 1 to 10 carbon atoms, a phenyl group AO, BO: an oxyalkylene group having 2 to 5 carbon atoms AO and BO are a block and / Or random m, n: an integer of 0 to 100. However, the compound represented by 100 ≧ m + n ≧ 4 is polyoxyethylenediamine,
Glycidol, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-to polyoxyalkylene diamines such as polyoxypropylene diamine and polyoxyethylene oxypropylene diamine
Glycidyl ether adducts such as methyl octyl glycidyl ether and sec-butylphenol glycidyl ether.

The oxyalkylene portion of the polyoxyalkylenediamines preferably has 2 to 5 carbon atoms. If the number of carbon atoms exceeds 5, the water solubility decreases, and not only cocondensation becomes difficult, but also an excellent flow effect cannot be obtained, which is not preferable. This oxyalkylene may be one type,
Two or more kinds of oxyalkylene may be bonded in a block or random manner. The number of repeating units is preferably 4 to 100, and more preferably 7 to 70. If the number of repeating units is less than 4, the resulting cement admixture may not have sufficient flow effect and may not have sufficient slump loss suppression effect, which is not preferable. Further, if the number exceeds 100, the cocondensation may not proceed well, which is not preferable.

In the case of alkyl glycidyl ethers among the glycidyl ethers, the number of carbon atoms in the alkyl moiety is preferably 1-10, more preferably 1-6. When the number of carbon atoms exceeds 10, when alkyl glycidyl ethers are used, even if a formaldehyde co-condensate is produced using the obtained adduct and used as a cement admixture, the hydrophobic part is large, so sufficient flowability is obtained. It is not preferable because the effect cannot be obtained.

The glycidyl ether adduct (A) to the polyoxyalkylenediamine represented by the general formula (1) can be obtained by a known method. That is, for example, in a container equipped with a stirrer, a thermometer, a reflux pipe, and a dropping funnel, under a nitrogen atmosphere, glycidyl ether is added dropwise to the polyoxyalkylenediamine under stirring, and 50
It can be easily obtained by reacting at ˜90 ° C. for 1 to 10 hours. The amount of glycidyl ether added at this time is preferably the number of moles bonded to one of the four active oxygen atoms at the terminals of the polyoxyalkylenediamine, or a slight excess amount.

The step of adding the compound represented by the general formula (1) may be preliminarily charged in the reaction apparatus at the start of the reaction for producing the formaldehyde cocondensate, or the pH may be adjusted.
When is subjected to the formaldehyde co-condensation reaction under the condition of a weakly acidic region, it may be added immediately before or immediately after the pH adjustment.

The compounds represented by the general formula (1) can be used in combination of one or more kinds. Furthermore, the addition amount thereof is 0.005 with respect to 1 mol of the monomer (B) capable of co-condensing the glycidyl ether adduct (A) with polyoxyalkylenediamine.
Is preferably 0.5 to 0.5 mol, more preferably 0.01 to 0.35 mol. The compound represented by the general formula (1) is
When it is less than 005 mol, the slump loss suppressing effect is not sufficiently exhibited, which is not preferable. Further, if it exceeds 0.5 mol, it becomes difficult to control the reaction, and further it becomes economically disadvantageous, which is not preferable.

The monomer (B) capable of co-condensing polyoxyalkylenediamine and formaldehyde is represented by the general formula (11) Compounds represented by, that is, melamine, methylol group-containing melamine, sulfomethyl group-containing melamine, and the like can be used. In the case of sulphomethyl group-containing melamine, salts thereof can also be used. Salts include inorganic salts, i.e., alkali metal salts or alkaline earth metal salts such as potassium, sodium, and magnesium;
Alternatively, organic salts, that is, ammonium salts, monoethanolamine salts, diethanolamine salts, and the like can also be used.

Further, in addition, as a general formula (lll) The compound represented by, that is, alkylphenols such as phenol, cresol, pt-butylphenol, and pt-amylphenol, or their sulfonic acids or salts of sulfonic acids can be used.
As the salt, an inorganic salt or an organic salt thereof can be used as in the case of the general formula (11). Of these, phenol, phenolsulfonic acid and salts thereof are preferable from the economical and reactivity viewpoints.

Further, the general formula (IV) The compound represented by, that is, urea, methylol group-containing urea, and sulfomethyl group-containing urea can also be used. In the case of urea containing a sulfomethyl group, the general formula (11)
Inorganic salts and organic salts thereof can be used as well.

In the present invention, the general formula (11),
One or more kinds of the monomers represented by the general formula (lll) and the general formula (lv) can be used in combination.
It is preferable to use 1) from the viewpoint of economy and reactivity.

As the compound (C) which forms a sulfone group, known sulfonating agents such as sodium sulfite, sodium bisulfite, sodium pyrosulfite, sulfur dioxide and fuming sulfuric acid can be used. These sulfonating agents may be used when introducing a sulfomethyl group into a corresponding raw material of the general formula (11) or the general formula (IV) in advance,
The sulfomethyl group may be directly introduced into the cocondensate by acting after synthesizing the cocondensate with formaldehyde.

The sulfomethyl group can be introduced into melamine by a known method. That is, it can be introduced by addition-condensing melamine with formaldehyde to obtain methylolmelamine, and then actuating a sulfonating agent to replace it with a hydroxyl group. It is known that 1 mol of melamine is subjected to addition condensation of 6 mol of formaldehyde as a methylol group. In the present invention, since 2 moles of methylol groups are likely to be used for cocondensation, sulfomethyl groups can be introduced into the remaining 4 moles of methylol groups at the maximum. Considering the economical aspect and the flow effect of the obtained cocondensate, the amount of the sulfomethyl group introduced is preferably 0.3 to 4 mol, and 0.5 to 2
More preferred is the introduction of moles.

The same applies to the case of introducing a sulfomethyl group into urea, preferably 0.3 to 2 mol, and more preferably 0.5 to 1.5 mol, per mol of urea. The formaldehyde used in synthesizing these formaldehyde cocondensates is usually 30 to 60.
It is possible to use a concentration of weight%. Further, if necessary, paraform can be used in combination. The amount of formaldehyde used is the glycidyl ether addition product (A) to polyoxyalkylenediamine.
It is preferable to use 1 to 6 times the total number of moles of the monomer (B) capable of co-condensing with formaldehyde. In consideration of economy, ease of the condensation reaction, and the like, it is more preferable to use 1.5 to 4 moles.

The formaldehyde co-condensation reaction is carried out at pH 4-1.
In the range of 2, the so-called weakly acidic region to the basic region is usually used. When the pH is less than 4, the condensation reaction may rapidly progress and gelation may occur, which is not preferable because the reaction cannot be controlled. Regarding the order of addition of formaldehyde, the reaction may be carried out in advance by charging the reactor or by dropping formalin.

The composition of the co-condensate that constitutes the cement admixture in the present invention is important. That is, glycidyl ether adduct to polyoxyalkylenediamine (A): glycidyl ether adduct to polyoxyalkylenediamine (A) and formaldehyde co-condensable monomer (B): compound that produces a sulfone group ( C):
The molar ratio of formaldehyde is (0.005 to 0.
5): 1: (0.3 to 4): (1 to 6) is preferable. More preferably, (0.01-0.35):
1: (0.5-2) :( 1.5-4) is preferable.

Next, an example of a specific method for producing the cement admixture in the present invention will be shown below, but the present invention is not limited to this. Specific Example 1 Polyoxyalkylenediamines were placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a dropping funnel, and in a nitrogen atmosphere at 20 to 80 ° C., an equimolar amount to the polyoxyalkylenediamines. The glycidyl ethers of are added dropwise from the dropping funnel over 0.5 to 2 hours, and further 50 to 90
The reaction is carried out at a temperature of 1 to 10 hours. By this operation, the glycidyl ether adduct (A) to the polyoxyalkylenediamine represented by the general formula (1) can be obtained.

Specific Example 2 The compound represented by the general formula (11), formaldehyde and water were charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel, and the temperature was raised to 60 to 90 ° C. rear,
The reaction is carried out under basic condition for 0.5 to 2 hours. Next, the compound represented by the general formula (111) was charged, and the amount was further adjusted to 60 to 9
The mixture is reacted at 0 ° C for 0.5 to 2 hours, then cooled to 30 to 50 ° C, and the compound represented by the general formula (IV) is added dropwise from the dropping funnel over 10 to 2 hours. Further, after reacting at 50 to 90 ° C. for 0.5 to 2 hours, general formula (1) and a compound (C) which forms a sulfonic group are added, and 0.5 at 60 to 90 ° C.
Let react for ~ 3 hours. Furthermore, the system is made weakly acidic to 50
The reaction is allowed to proceed until the viscosity of the solution reaches a predetermined value at -80 ° C. When the viscosity of the solution reaches a predetermined value, it is neutralized to stop the reaction. The predetermined viscosity for stopping the reaction depends on the non-volatile content of the solution, but when the non-volatile content is 35%, the value measured by the B-type viscometer is 10 to 500 cp / 25 ° C.
Is preferable and 15-300 cp / 25 degreeC is more preferable. When the viscosity is out of this range, even if the obtained co-condensate is added to the cement composition, the flow effect and the slump loss suppressing effect may not be sufficiently exhibited.

The compound represented by the general formula (1) may be charged at any time as long as it is a step prior to immediately after changing the liquid property in the system to weakly acidic. That is, when the initial water was charged, before and after the addition of the general formula (lll), the general formula (lv)
Can be added before or after the dropwise addition of the compound (C), before or after the addition of the compound (C) that generates a sulfone group, and immediately before or after the liquid property in the system is changed to weakly acidic.
Further, for the purpose of cooling, the charged water may be divided into the respective steps, or the addition of each compound may be divided and added. Furthermore, you may change the addition order of each compound.

Specific Example 3 A compound represented by the general formula (1), the general formula (11) and the general formula (111), formaldehyde, water, and a compound (C) which produces a sulfo group are mixed with a stirrer, a thermometer, A 4-necked flask equipped with a reflux tube was charged, and the mixture was heated to 60-
The reaction is carried out at 90 ° C for 0.5 to 5 hours. Furthermore, the inside of the system is set to a weakly acidic region and the reaction is performed at 40 to 80 ° C. for 0.5 to 10 hours. When the viscosity of the solution reaches a predetermined value, it is neutralized to stop the reaction. The specific viscosity for stopping the reaction is Specific Example 2
Same as. Further, as in the case of Example 2, the compound represented by the general formula (1) may be charged any time as long as it is before the step immediately after changing the liquid property in the system to weakly acidic.

The cement admixture of the present invention can be used in combination with other conventionally known AE water reducing agents, high performance water reducing agents, and high performance AE water reducing agents. That is, β-naphthalene sulfonic acid formaldehyde high condensate salt, melamine sulfonic acid formaldehyde condensate salt, amino sulfonic acid condensate salt, lignin sulfonic acid salt, oxycarboxylic acid, polycarboxylic acid type water reducing agent, alkali hydrolysis It can be used in combination with a type water reducing agent, a sustained release high performance water reducing agent, and the like.

Regarding the method of using the cement admixture of the present invention, other known cement admixtures such as air entraining agent, defoaming agent, setting accelerator, setting retarder, rust preventive, antiseptic, waterproofing agent, strength It is also possible to use it together with a promoter or the like. In addition, the method of use is usually mixed in kneading water and added to the cement composition.However, the method of adding the cement composition at once or adding it separately at the time of preparing the cement composition, the method of adding the cement composition after kneading, Any method such as the method of adding may be used.
The cement admixture according to the present invention varies depending on the composition and use of the cement composition, but is usually 0.01 to 2.0% by weight, preferably 0.0 to 2.0% by weight in terms of solid content with respect to the cement.
It is used in a proportion of 5 to 1.0% by weight. Usage is 0.0
If it is less than 1% by weight, the dispersion fluidity tends to decrease and the slump loss preventing effect tends to decrease. On the other hand, if it exceeds 2.0% by weight, it tends to cause material separation, making it difficult to obtain a homogeneous cured product, and is economically disadvantageous.

The cement admixture according to the present invention can be applied to concrete and mortar prepared by using various Portland cement, fly ash cement, blast furnace cement, silica cement, various mixed cements and the like.

The reason why the cement admixture of the present invention exhibits excellent flow effect, slump loss suppressing effect, and material separation resistance without showing retardation of setting is not clear, but it is presumed as follows. That is, since the cement admixture of the present invention has a sulfone group in the molecule similarly to the conventional high-performance water reducing agent, the dispersibility of the cement particles is enhanced by its electric repulsion. Further, when the cement admixture of the present invention is adsorbed on the cement particles, it is considered that the polyoxyalkylene group in the molecule extends to the outside of the cement particles. It is considered that a hydration layer is formed around the polyoxyalkylene group extending to the outside, and the steric hindrance effect associated therewith holds the dispersibility of the cement particles for a long time and suppresses slump loss. Furthermore, the conventional sustained-release high-performance water reducing agent,
Unlike polycarboxylic acid type water reducing agents and alkaline hydrolysis type water reducing agents, since they do not have a carboxyl group having a high chelating ability with Ca ions in the molecule, they are not expected to show a setting retarding property. Therefore, the cement admixture of the present invention has excellent dispersion performance, slump loss suppressing effect, and material separation resistance.

The cement admixture of the present invention will be described in more detail in the following examples, but the present invention is not limited thereto. In addition, all percentages or parts described below as units of numerical values are% by weight or parts by weight unless otherwise specified.

[0034]

EXAMPLES Synthesis of Glycidyl Ether Addition Product (A) to Polyoxyalkylenediamine Table 1 shows the physical property values of the polyoxyalkylenediamines used in the present invention. As a typical polyoxyalkylene diamine,
JEFFAMINE D manufactured by San Techno Chemical Co., Ltd.
Series, ED series, and PE manufactured by NOF CORPORATION
G-1000 diamine and PEO amine # 6000 manufactured by Kawaken Fine Chemicals Co., Ltd. were used. When describing these compounds below, JEFFAMIN
ED series and ED series are simply D-23
0, D-400, D-2000, D-4000, ED-
600, ED-900, ED-2001, those produced by NOF CORPORATION are simply described as PEG-1000, and those produced by Kawaken Fine Chemical Co., Ltd. are simply described as PEO amine.

[0035]

[Table 1] * 1 PO / EO is the ratio of propylene oxide and ethylene oxide contained in the molecule. * 2 Molecular weight is the molar weight average molecular weight.

Synthesis Example 1 0.1 mol (100 parts) of PEG-1000 was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a dropping funnel, and mixed under stirring in a nitrogen atmosphere. 70 ℃
The temperature was raised to, and 0.1 mol (13.2 parts) of butyl glycidyl ether was added dropwise from the dropping funnel over 20 minutes. This was reacted for a further 3 hours and then cooled to obtain a synthetic product. This was designated as adduct 1.

Synthetic Examples 2 to 13 The same operations as in Synthetic Example 1 were carried out by changing the combinations shown in Table 2 to obtain adducts 2 to 13.

[0038]

[Table 2]

Production Example 1 Melamine 0.67 mol (84.4 parts), 37% formalin 3.0 mol (244.5 parts) and water 200.0 parts were added to a stirrer, a thermometer, a reflux tube and a dropping funnel. The mixture was placed in a four-necked flask which had been prepared, and mixed with stirring. After the temperature was raised to 65 ° C., the pH was adjusted to 11.5 with a 25% aqueous sodium hydroxide solution.
The reaction was performed at 65 ° C. for 1 hour. Add 0.2 mole of urea (1
2.1 parts) was added, and the mixture was reacted at 70 ° C. for 1 hour. Next, 190.4 parts of water was added, and at the same time, the mixture was cooled to 45 ° C., and 0.13 mol (12.6 parts) of phenol was added over 30 minutes using a dropping funnel. After charging
The reaction was carried out at 60 ° C for 1 hour. Subsequently, 0.03 mol (37.8 parts) of the adduct 1 obtained in Synthesis Example 1 and 0.53 mol (55.7 parts) of anhydrous sodium bisulfite were added, and 8
The reaction was performed at 0 ° C. for 1 hour. After cooling to 60 ° C, 40
% Sulfuric acid to pH 6.0, raise the temperature to 65 ° C., and react.
When the viscosity of the reaction solution reaches 50 cp / 25 ° C, 2
The reaction was stopped by neutralizing with a 5% aqueous sodium hydroxide solution, and the obtained product was designated as cocondensate 1. The composition and physical property values are shown in Table 3.

Production Example 2 628.2 parts of water, 3.1 mol of 37% formalin (25 mol)
(3.4 parts) was placed in a four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, and mixed with stirring. In this flask, 0.63 mol of melamine (78.8 parts), 0.38 mol of urea (22.5 parts), 0.5 mol of sodium pyrosulfite (9 parts)
5.0 parts) and the adduct 2 obtained in Synthesis Example 2 were added under stirring with 0.13 mol (134.2 parts). This one 75
After confirming that the temperature rises to ℃ and it becomes a transparent liquid,
Adjust the pH to 11 with a 25% aqueous sodium hydroxide solution, then 75 ° C
For 2 hours. After confirming that free sulfite ions had disappeared, the mixture was cooled to 60 ° C. Then 40%
The pH of the reaction mixture was adjusted to 6.0 with sulfuric acid, the reaction was allowed to proceed at 60 ° C, and when the viscosity of the reaction solution reached 50 cp / 25 ° C, the reaction was stopped by neutralizing with 25% aqueous sodium hydroxide solution. Was designated as Cocondensate 2. The composition and physical property values are shown in Table 3.

Production Example 3 457.7 parts of water, 2.8 mol of 37% formalin (22
(5.9 parts) was charged into a four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, and mixed by stirring. To this flask, 1.0 mol (125.4 parts) of melamine and 0.1 mol (108.3 parts) of the adduct 3 obtained in Synthesis Example 3 are added under stirring. This was heated to 70 ° C., and after confirming that a transparent liquid was obtained, p was added with a 25% aqueous sodium hydroxide solution.
H11 and reacted at 70 ° C. for 1 hour. Then cool to 55 ° C. and add anhydrous sodium bisulfite 0.8 (82.8).
Parts). Although the internal temperature increased by the addition of anhydrous sodium bisulfite, the temperature was further increased to 80 ° C. 80 ℃
The reaction was continued with, and after it was confirmed that free sulfite ion had disappeared, the mixture was cooled to 60 ° C. Next, the pH was adjusted to 6.0 with 40% sulfuric acid, the reaction was allowed to proceed at 60 ° C., and when the viscosity of the reaction solution reached 140 cp / 25 ° C., the reaction was terminated by neutralization with a 25% aqueous sodium hydroxide solution to obtain The obtained product was designated as cocondensate 3. The composition and physical property values are shown in Table 3.
Shown in

Production Examples 4 to 6 In the same manner as in Production Example 1, using the adducts 4 to 6 obtained in Synthesis Examples 4 to 6 and varying the composition of the compound as shown in Table 3, condensation was tried. It was As a result, cocondensates 4 to 6 were obtained.

Production Examples 7 to 9 In the same manner as in Production Example 2, using the adducts 7 to 9 obtained in Synthesis Examples 7 to 9 and varying the composition of the compound as shown in Table 3, condensation was tried. It was As a result, cocondensates 7 to 9 were obtained.

Preparative Examples 10 to 13 In the same manner as in Preparative Example 3, using the adducts 10 to 13 obtained in Synthetic Examples 10 to 13 and varying the composition of the compound as shown in Table 3, condensation was tried. It was As a result, the cocondensate 10-
13 was obtained.

Production Example 14 Except that the compound represented by the general formula (1) was not used,
Condensation was tried by changing the composition of the compound as shown in Table 3 in the same manner as in Production Example 1. As a result, a cocondensate 14 was obtained.

Production Examples 15 to 16 Using the adduct 1 obtained in Synthesis Example 1, the composition of the compound was changed as shown in Table 3 in the same manner as in Production Example 1 to attempt condensation. As a result, cocondensates 15 to 16 were obtained.

[0047]

[Table 3]

Example 1 Using a 50-liter forced twin-screw concrete mixer, based on the composition shown in Table 4, cement, coarse aggregate, and the mixture obtained in Production Example 1 were used so that the kneaded amount was 40 liters. The condensate 1 and water were added, and the mixture was kneaded for 90 seconds, and further coarse aggregate was added and kneaded for 3 minutes. A fluidized concrete having a slump of 18 cm and an air content of 3% was prepared. In order to reach the target air volume, if the entrained air volume is insufficient, use the air entrainer Vinsol manufactured by Yamamune Chemical Co., Ltd.
When the amount of air was excessive, it was adjusted using Dereklite 850 manufactured by Hokucon Sangyo Co., Ltd. as an antifoaming agent. After kneading, slump and slump flow with time were measured every 30 minutes until 90 minutes later. The compressive strength is φ10
Cylinder type test piece of 20 cm in height and 20 cm in height was prepared, and 7 days a day
The measurement was performed on the 28th day. Regarding the material separation resistance, the degree of movement of the aggregate during slump flow measurement was visually observed, and relative evaluations of ◎, 、, Δ, and × were made. In addition, the method of measuring the slump, the amount of air, the setting time and the compressive strength, and the method of preparing the specimen for compressive strength were all based on Japanese Industrial Standards (JIS-A6204). Table 5 shows the results
Shown in

[0049]

[Table 4] W / C: Water / cement (wt%) s / a: Fine aggregate / fine aggregate + coarse aggregate (volume%) C: Cement W: Water S: Fine aggregate G: Coarse aggregate

Material for concrete kneading Cement: Three kinds of ordinary Portland cement (Mitsubishi Materials Corp., Chichibu Onoda Co., Ltd., Tokuyama Corp.) Specific gravity = 3.16 Fine aggregate: Irino produced by Kawachi-cho, Kamo-gun, Hiroshima Prefecture Granite mountain sand Specific gravity = 2.57 Coarse aggregate: Hard sandstone crushed stone from Masuishi, Shimonoseki City, Yamaguchi Prefecture, Ishihara character Crushed stone 5: Crushed stone 6 = 1: 1 Specific gravity = 2.69

Examples 2 to 13 The same operations as in Example 1 were carried out except that the condensates 2 to 13 were used. Table 5 shows the results.

Comparative Examples 1 to 3 The same operations as in Example 1 were performed except that the condensates 14 to 16 were used. Table 5 shows the results.

Comparative Examples 4 to 8 As a water-reducing agent for comparison, a commercially available high-performance water-reducing agent, Melflow 40 (Mitsui Toatsu Chemicals, Inc .: melamine type),
Mighty 150 (Kao Corporation: naphthalene type), Palic FP200U (Fujisawa Pharmaceutical Co., Ltd .: aminosulfonic acid type), sustained release type Mighty 2000WH which is a high performance AE water reducing agent (Kao Corporation: naphthalene type + The same operation as in Example 1 was performed using Tupole HP-8 (Takemoto Oil & Fats Co., Ltd .: polycarboxylic acid system). Table 5 shows the results.

[0054]

[Table 5]

[0055]

As is clear from the examples and comparative examples, the cement admixture obtained according to the present invention shows a high flow effect at a low addition amount and a residual flow as compared with the existing cement water reducing agent. It has the characteristics of high rate and excellent daily strength. That is, it has a high initial fluidity and an excellent slump retention property for a cement composition such as mortar and concrete without causing a hardening delay. Furthermore, the material separation resistance is also excellent. Therefore, when the cement admixture obtained by the present invention is used for civil engineering and construction-related works, workability can be significantly improved.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshihiko Tomita 7-1-1, Hikoshimasako-cho, Shimonoseki-shi, Yamaguchi Pref.

Claims (7)

[Claims] 1. A glycidyl ether adduct (A) to polyoxyalkylene diamine, a glycidyl ether adduct (A) to polyoxyalkylene diamine, a monomer (B) capable of formaldehyde co-condensation, and a sulfone group. A cement admixture comprising a co-condensate containing the resulting compound (C) and formaldehyde. 2. The cement admixture according to claim 1, wherein the glycidyl ether adduct (A) to polyoxyalkylenediamine is represented by the following general formula (1). General formula (l) Here, R ₁ : an alkyl group having 1 to 5 carbon atoms R ₂ : H, an alkyl group having 1 to 10 carbon atoms, a phenyl group AO, BO: an oxyalkylene group having 2 to 5 carbon atoms AO and BO are a block and / Or random m, n: an integer of 0 to 100. However, 100 ≧ m + n ≧ 4 3. A glycidyl ether adduct (A) to polyoxyalkylenediamine and a monomer (B) capable of formaldehyde co-condensation are composed of melamine or its derivative, phenol or its derivative, and urea or its derivative. The cement admixture according to claim 1, which is one kind or two or more kinds of compounds selected from the group. 4. A compound (C) which forms a sulfone group
2. The cement admixture according to claim 1, wherein the cement admixture comprises one or more compounds selected from the group consisting of sodium sulfite, sodium bisulfite, sodium pyrosulfite, fuming sulfuric acid, and sulfur dioxide. 5. The cement admixture according to claim 3, wherein melamine or a derivative thereof is represented by the following general formula (11). General formula (11) 6. The cement admixture according to claim 3, wherein the phenol or its derivative is represented by the following general formula (111). General formula (Ill) 7. The cement admixture according to claim 3, wherein urea or a derivative thereof is represented by the following general formula (IV). General formula (LV)